US20130328234A1 - Polytitanic acid esters and use thereof to produce implantable, optionally absorbable fibers - Google Patents
Polytitanic acid esters and use thereof to produce implantable, optionally absorbable fibers Download PDFInfo
- Publication number
- US20130328234A1 US20130328234A1 US13/985,755 US201213985755A US2013328234A1 US 20130328234 A1 US20130328234 A1 US 20130328234A1 US 201213985755 A US201213985755 A US 201213985755A US 2013328234 A1 US2013328234 A1 US 2013328234A1
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- US
- United States
- Prior art keywords
- compound
- titanium
- acid
- water
- acid esters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 37
- 239000002253 acid Substances 0.000 title claims abstract description 26
- 150000002148 esters Chemical class 0.000 title claims abstract description 18
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Images
Classifications
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
- C07C59/06—Glycolic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
- C07C59/08—Lactic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
Definitions
- the present invention relates to polytitanic acid esters as well as a spinnable mass that can be produced by means of hydrolysis and condensation of a titanium coordination compound having fewer than two 2-hydroxy carboxylic acid anions per titanium atom and which contains said mass.
- the mass can contain water-soluble poly propionic acid-2-oxo-titanium oxide hydrate or a salt thereof.
- Fibers spinnable thereof can be used as resorbable implant material in the field of medical engineering, for example as scaffolds for the regeneration of bone, cartilage or soft tissue cells.
- Resorbable implants have been used in the field of implantology for many years. Resorbable biomaterials became known in connection with the development of resorbable sutures on the basis of synthetically manufactured polylactides (PLAS) and polyglycolides (PGLAs) in the 1970s of the last century. In a next generation, this material was used to produce implants such as screws and plates to fixate tissue and bones. As the know-how about the material properties, degradation behavior and feasibility of different clinical indications increased, the first vessel supports (stents), soft tissue reinforcement implants (e.g. hernia repair mesh patches) and membrane systems, such as they are used among other things for jaw surgeries, were successfully manufactured in the 1990s. Other, more recent examples include hydrogen-filled tubes used as so-called nerve conduction guides for neuronal regeneration or cell carrier structures used in the field of tissue engineering.
- PLAS polylactides
- PGLAs polyglycolides
- Carrier materials used for tissue engineering usually contain organic, resorbable polymers (PLAs/PGLAs) as basic component.
- PHAs/PGLAs organic, resorbable polymers
- the original stability of the structure and hence the shape is initially achieved with the resorbable supporting body.
- the problem with resorbable implants according to the prior art is the fact that the implant is identified as foreign body by the recipient due to its material, thus inducing a sterile immune response. Indeed, this does generally not cause rejection reactions like those observed with allogeneic (i.e. originating from a human donor) or xenogeneic (originating from an animal donor) organ implants; however, it can interfere with the adhesion and growth of the body's own cells in the region of the implant.
- Resorbable implants such as suture materials made of PLA have been improved with the application of a very thin, non-resorbable titanium coat.
- the non-resorbable coat only partly covers the resorbable material.
- the adhesion and growth of the body's own cells are promoted in the coated area, thus facilitating a faster healing process.
- the resorption is slowed down on the coated part of the implant, see EP 1 752 167 E1.
- Biodegradable or resorbable fibers with the formal chemical composition Si n (OH) 2x O 2n ⁇ x were produced at the Fraunhofer Institute for Silicate Research.
- the mechanical properties of composite materials produced with the fibers, for example a resorbable wound dressing, are clearly superior to those of pure polymer compact materials.
- the wound dressing maintains its support function for a considerably longer period of time than a traditional organic implant.
- the cell adhesion and proliferation are not impaired.
- the degradation rate (solubility) is determined by the silanol content which can be adjusted with the manufacturing parameters (water content, storage).
- Fibers made of commercially available titanium-bis-(ammonium lactato)-dihydroxide in combination with polyvinyl alcohol (PVA) as spinning additive can be produced by means of an electrospinning procedure.
- TiO 2 fibers suitable for photocatalytic purposes K. K. Nakane et al., Journal of Applied Polymer Science, Vol, 104, 1232-1235 (2007)) were produced from said fibers by means of calcination.
- the electrospinning procedure was used by T. Schiestel at the Fraunhofer institute for Interfacial Engineering and Biotechnology (IGB) for the manufacture of ultra-thin fibers.
- the jet of a fluid is accelerated in the electrical field and continuously split into additional rays which mutually repel each other due to the like charges.
- the solvent evaporates during the spinning process, ultimately creating polymer fibers with diameters in the sub-micrometer and nanometer range.
- Electrospinning can be used for a variety of materials including polyvinylpyrrolidone (PVP), PEO or PLA.
- JP 62223323 (1987) describes an alcoholic titanium oxide solution which is hydrolyzed and condensed with hydrochloric acid. Said solution can allegedly be used to spin fibers. They are heated to obtain titanium oxide fibers.
- a similar method is described in EP 1 138 634 B1.
- the information contained in this printed document was not reliably reproducible.
- the inventors of the present application determined that the aqueous hydrolysis of isopropoxy titanate under the conditions described in EP 1 138 634 B1 yields a suspension which cannot be reduced to a spinnable mass. This is not surprising because it is generally known that titanium alkoxides instantly condense hydrolytically with the addition of water, wherein ring-shaped or three-dimensional clusters are formed.
- Textile structures made of resorbable fibers are frequently used as medical implants to help support or replace soft and hard tissue.
- the suitable process management and selection of the fiber material makes it possible to achieve a large variety of surfaces, porosities and mechanical anisotropies to mimic the unique structural and mechanical properties of biological tissues.
- Current applications include wound care (fleece), wound closure (suture materials), hernia repair mesh patches and receptacles (knits) as well as cell carrier systems to grow bone, skin, cartilage, tendons or liver tissue in vitro.
- titanium is a widely used material for resorbable implants.
- endoprostheses with titanium shafts and acetabular cups made of titanium are implanted annually around the world.
- Titanium owes its favorable biotolerance to the only several nanometers thin oxide hydrate layer at the surface.
- Human osteoblast cells literally spread out on it, firmly anchoring with the material, thus creating direct contact with the bone. Fibroblasts propagate unhindered and grow all the way to edges of implants made of titanium passivated with titanium oxide, see Kohler S.
- lactic acid (2-hydroxypropionic acid) are likewise widely used in the field of medical engineering. in this respect, reference is made for example to Lucke, A., J. Tessmar, at al. Biodegradable poly(D,L-lactic acid)poly(ethylene glycol)-monomethyl ether diblock copolymers: structures and surface properties relevant to their use as biomaterials, Biomaterials 21(23) (2000) 2361-70.
- PLA is used for a number of medical applications due to its biocompatibility and degradability in the human body.
- PLA often combined with a copolymer, is a suitable suture material. However, it is also used to manufacture nails and screws, plates or slants. Irrespective of the chemical composition and porosity, FLA can remain in the body for a few months to several years, until it is broken down.
- Titanium complexes with lactic acid have already been described in U.S. Pat. No. 2,870,181; their usability as gelling agent for polyhydroxy compounds such as starch and polyvinyl alcohol is discussed there.
- the invention was based on the task to develop a resorbable implant material which on the one hand can be brought into the form of fibers and on the other hand combines several benefits of resorbable organic implant materials made of poly-( ⁇ -hydroxy carboxylic acids) such as PLA on the one hand and titanium oxide hydrate surfaces on the other hand.
- the inventors complexed a titanium starting material such as titanium tetraethylate with an ⁇ -hydroxy carboxylic acid to create a hydrolytically stable oxo compound of titanium which can hence be used in aqueous media.
- Said compound was mixed with a known spinning additive such as polyvinyl alcohol, polyacrylic acid or polyethylene oxide, and an attempt was made to form fibers hereof by extruding the created mass through nozzles.
- a known spinning additive such as polyvinyl alcohol, polyacrylic acid or polyethylene oxide
- titanium compounds Two titanium compounds are known in which the titanium atom is complexed with the ⁇ -hydroxy carboxylic acid lactic acid, namely titanium-bis-(ammonium lactato)-dihydroxide (see H. Mockel at al., J. Mater, Chem., 1999 (99), 3051-3056), marketed as 50% aqueous solution, and ammonium trilactatotitanate (Inorg. Chem. 2004, vol. 43, 4546-4548). Based on information from the authors, the first of the two molecules has a monomeric structure with two chelating complexing ammonium lactate anions and two bound hydroxyl groups.
- the latter molecule which is also water-soluble, exists at least in the solid state in the form of a monomeric compound complexing with three lactate molecules, wherein all three lactate molecules form a 5-membered ring with the titanium atom via bidentate oxygen. Accordingly, it does not comprise any potential substituents, e.g. an OH or alcoholate group which would allow oligomerization. Therefore, said compound had to be discounted from the start.
- titanium-bis-(ammonium lactato)-dihydroxide carries two hydroxy groups and can therefore condensate to form polymer chains. They are necessary to obtain a spinnable material without spinning additives.
- the OH groups at the Ti atom apparently only condensate to a minor degree due to two ammonium lactato substituents at the central Ti atom, and the steric hindrance is so strong that the oligormerization is insufficient to achieve a stable thread formation.
- the titanium compound is reacted with the compound (II) at a molar ratio of 1 to 0.5-1.9, preferably of 1 to 0.7-1.5, with respect to an unbridged titanium compound, i.e., a (monomeric) titanium compound containing a single titanium atom, and optionally a subsequent hydrolysis of the formed chelate complex to facilitate the required condensation processes.
- an unbridged titanium compound i.e., a (monomeric) titanium compound containing a single titanium atom
- water will be added for this purpose during or after the reaction with the compound containing the mentioned structural unit.
- Titanic acid esters with at least in part only one of the structural units defined above per titanium atom as well as hydroxyl groups bound at the titanium atom are formed in the process.
- Titanic acid esters with only one structural unit as described above have the theoretical formula Ti(O ⁇ CR 4 —(CR 5 R 3 ) p —CR 1 R 2 —O)(OH) 3 . They can form oxo bridges with other titanium atoms in the known fashion, meaning that they are free for at least partial linear polymerization.
- the polymeric titanic acid esters are created with this condensation reaction; they are available as viscous mass from which stable threads can be spun by means of a spinning nozzle, optionally after removing part of the solvent in which they were produced.
- the structural element is a component of a hydroxy carboxylic acid.
- the substituents and indices are defined as follows: R 1 is hydrogen, alkyl or alkenyl, preferably hydrogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkenyl, particularly preferably hydrogen or C 1 -C 4 -alkyl, R 2 is hydrogen, alkyl or alkenyl, preferably hydrogen, methyl or ethyl, and R 3 and R 5 independently are hydrogen or an unsubstituted alkyl or alkenyl or an alkyl or alkenyl preferably substituted with OH, more preferably having 1 to 4 carbon atoms each.
- R 5 is a methyl or ethyl ; optionally substituted with hydroxy in this case.
- the compound with the mentioned structural unit is glycolic acid (2-hydroxyethanoic acid), lactic acid (2-hydroxypropionic acid), 2-hydroxybutyric acid, 2-hydroxyisobutyric acid or 2,2-bis(hydroxymethl)propionic acid.
- alkali or ammonium carboxylate-2-oxotitanate trihydroxide The compound created during the exchange of the free acid proton with an alkali or ammonium cation can then be referred to as alkali or ammonium carboxylate-2-oxotitanate trihydroxide.
- a spinnable mass can be obtained both from compounds with a complexed carboxylic acid group as well as from compounds with a complexed cation carboxylate group by way of hydrolysis, said mass likely containing the corresponding poly(carboxylic acid-2-oxo-titanium oxide hydrate) and poly(alkali- or ammoniumcarboxylate-2-oxotitaniurn oxide hydrate) created with linear polymer chains.
- Said types of polymers are herein referred to as polytitanic acid esters.
- the structural unit is part of a keto- or aldo-carboxylic acid.
- R 1 and R 2 together mean ⁇ O
- R 4 is alkyl or alkylen, preferably having 1 to 16 carbon atoms and hydrogen, while the remaining groups and indices have the same meaning as in the first variant.
- R 3 and R 5 can advantageously both be hydrogen.
- acids that can be used include pyruvic acid (2-oxopropanoic acid) and glyoxylic acid (oxoethanoic acid).
- alkyl, alkenyl and alkylen groups of the present invention can be provided independently from each other as straight chains, in branched or cyclical form. They can be substituted or unsubstituted.
- the index p is 0 in a preferred embodiment relating to both variants.
- titanium-based starting compound Any titanium compounds in which titanium is present in formally quadrivalent form are suitable as titanium-based starting compound. Compounds in which no more than 2 OH groups are present are preferred. Purchasable titanium alicylates (titanium alkoxides) such as titanium ethylate Ti(OC 2 H 5 ) 4 are advantageous. Titanium compounds without free hydroxy groups are particularly preferred.
- the molar ratio of a (monomeric) titanium compound to the compound (II) containing the mentioned structural unit is preferably in the range of 1 to 0.7-1.5, more preferably in the range of 1 to 0.9-1:1 and most preferably in the range of 1:1 in the process, it was determined that in cases where less than 0.5 mol, in some cases also less than 0.7 mol of the compound containing the structural unit was used per mol of titanium, no reaction product soluble in water was obtained, and it was therefore impossible to draw threads. With a ratio of more than 1.9 mol of compound containing the structural unit per mol of titanium, no masses were produced from which it was still possible to draw threads.
- a monocarboxylic acid is additionally added to the reaction, it is recommended that the molar ratio of (monomeric) titanium compound to the sum of compound (II) and the monocarboxylic acid is likewise in the upper range for the ratio of titanium compound to compound (II) or that it only falls slightly short of it.
- the reaction generally takes place in suspension, preferably in an alcohol or an alcohol-water mixture and optionally directly in water.
- Alkyl alcohols that are liquid at room temperature and optionally at temperatures up to at least 60° C. such as methanol, ethanol, n- or i-propanol or n-, i- or t-butanol are preferably used as alcohols.
- optionally (and less preferably) other polar solvents alone or mixed with the ones mentioned above, can be used. Examples are ketones such as acetone. Irrespective of the selection of the solvent, it can additionally contain acids, in particular organic acids such as lactic acid or a different acid usable for the invention, or a base such as e.g. ammonia.
- the hydrolysis is preferably carried out at a temperature ranging between 10 and 35° C., in particular at room temperature.
- the product is present in the selected solvent (mixture) in the form of a sometimes turbid, sometimes clear, gel-like solution. Said solution can be adjusted to the desired solid matter concentration and viscosity as needed, e.g.
- the viscous mass can be extruded through nozzles or drawn to create threads with a different method.
- nozzles with a diameter between 50 ⁇ m and 1000 ⁇ m are considered.
- the viscosity ranges between 30 and 250 Pa ⁇ s (20 ° C.). Preparations with higher viscosities can also be spun through smaller nozzle diameters (150 ⁇ m) after they have been heated to 40° C.
- the viscosity the range of 30-50 Pa ⁇ s has proven to be advantageous
- the concentration of the spinning mass and the nozzle diameter the diameters of the obtained fibers can be adjusted to a wide range, wherein a range from 5 to 200 ⁇ m is particularly advantageous.
- the created fibers can be wound up as continuous fibers, optionally after having been dried or, be stored otherwise, e.g. after having been cut, for instance in the form of a fleece.
- a drop distance advantageously with a length of several decimeters to meters is suitable to achieve the initial dryness.
- the fibers obtained by means of spinning are readily soluble in water and can dissociate into colloidal titanium oxide hydrate, the same compound as the one present on the surface of titanium implants, as well as the chelating compound or its salt if its acidic proton was exchanged for a salt cation.
- the chelating compound is a biocompatible or even a resorbable compound such as lactic acid or a salt thereof such as ammonium lactate, it can dissociate into catabolic products such as sodium or calcium lactate, optionally even by interacting with the body's own substances. These are substances generally recognized as safe by the Food and Drug Administration (FDA). These kinds of safe catabolic products can optionally also be created with the addition of calcium or magnesium hydroxide to the spinning preparations.
- the water solubility of the obtained fibers can be modified by exposing them to a specific temperature regimen. If they are exposed to more heat, their water solubility decreases. Heating them for several hours at temperatures ranging from 100 to 300° C., e.g. at 200° C. for approximately 20-30 hours, can render them completely insoluble in water.
- the fiber according to the invention can be produced in a pH-neutral form in one embodiment of the invention, such that it is neither expected to have any negative impacts on the tissue milieu with respect to its degradation products nor to induce any foreign body reactions. If the acidic material is used for the fiber instead, the acid group can be utilized for the linkup of active substances.
- Example 1.1 was repeated with the stipulation that the corresponding molar ratio of glycolic acid was used instead of lactic add.
- the reaction mixture heated by the exothermal reaction is stirred until it has cooled down to room temperature.
- the solvent is then removed from the mixture with a rotary evaporator in the water bath (50° C.) at a pressure of up to 40 mbar until a tough mass is created
- the quantity ratios mentioned above were varied in the range of 0.5 to 1.8 mol of lactic acid per mol of titanium compound. It was easily possible to spin threads from masses based on a quantity ratio between 0.7 and 1.5 mol of lactic acid per mol of titanium compound.
- Example 1.6 was repeated with the stipulation that glycolic acid was used instead of lactic acid.
- the manufacture was analogous to the examples 1.6 and 1.7, wherein however a mixture lactic acid and glycolic acid at a ratio of 1:0.5 was used.
- Variant b R 4 equals H; R 1 and R 2 together equal ⁇ O and p equals 0; 1 mol of glyoxylic acid (oxoethanoic acid); high water content,
- the viscous mass of examples 1.1 to 1.3 was in each case extruded through one or a plurality of 200 ⁇ m nozzles at a temperature of 25° C. and a pressure of 20 bar. After dropping 2.5 m, the fibers were reeled onto a rotating cylinder or set down in the form of a fleece using a jig table to horizontal surface movable in 2 dimensions).
- the fiber diameter generally ranges between 20 and 100 ⁇ m.
- a powder X-ray diffractogram of fibers obtained in this fashion according to example 1.1 is illustrated in FIG. 2 and one according to example 1.7 is illustrated in FIG. 3 . Both powder X-ray diffractograms do not show the main reflex typical for anatase at 25.32 theta.
- Fibers from the masses of example 1.1 were kept at 200° C. in air in a drying chamber. After a heating period of 2 h, several hours were required for 50 mg of fibers to dissolve in 10 mg of water at room temperature. After 24 h at 200° C., they were insoluble in water.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE102011011544A DE102011011544A1 (de) | 2011-02-17 | 2011-02-17 | Polytitansäureester und deren Verwendung zur Herstellung von implantierbaren, ggf. resorbierbaren Fasern |
DE102011011544.7 | 2011-02-17 | ||
PCT/EP2012/052513 WO2012110512A1 (de) | 2011-02-17 | 2012-02-14 | Polytitansäureester und deren verwendung zur herstellung von implantierbaren, ggf. resorbierbaren fasern |
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US20130328234A1 true US20130328234A1 (en) | 2013-12-12 |
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Application Number | Title | Priority Date | Filing Date |
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US13/985,755 Abandoned US20130328234A1 (en) | 2011-02-17 | 2012-02-14 | Polytitanic acid esters and use thereof to produce implantable, optionally absorbable fibers |
Country Status (4)
Country | Link |
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US (1) | US20130328234A1 (de) |
EP (1) | EP2675817B8 (de) |
DE (1) | DE102011011544A1 (de) |
WO (1) | WO2012110512A1 (de) |
Cited By (1)
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JPWO2019138989A1 (ja) * | 2018-01-12 | 2020-12-24 | 日本化学工業株式会社 | チタンキレート化合物の製造方法 |
Citations (1)
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US20060254461A1 (en) * | 2005-05-11 | 2006-11-16 | Agency For Science, Technology, And Research | Method and solution for forming anatase titanium dioxide, and titanium dioxide particles, colloidal dispersion and film |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US2870181A (en) * | 1954-02-17 | 1959-01-20 | Du Pont | Water soluble organotitanium compounds and process of preparation |
US4166147A (en) | 1973-04-16 | 1979-08-28 | Minnesota Mining And Manufacturing Company | Shaped and fired articles of tio2 |
JPS62223323A (ja) | 1986-03-20 | 1987-10-01 | Central Glass Co Ltd | 酸化チタン繊維の製造法 |
US6086844A (en) | 1996-12-26 | 2000-07-11 | Sumitomo Chemical Company, Ltd. | Titania fiber, method for producing the fiber and method for using the fiber |
DE60107991T2 (de) * | 2000-03-31 | 2005-12-15 | Sumitomo Chemical Co., Ltd. | Verfahren zur Herstellung von Titanoxid |
DE102005032604A1 (de) | 2005-07-13 | 2007-01-18 | Gfe Medizintechnik Gmbh | Resorbierbares, in den Körper einsetzbares medizinisches Element, insbesondere resorbierbares Implantat |
-
2011
- 2011-02-17 DE DE102011011544A patent/DE102011011544A1/de not_active Withdrawn
-
2012
- 2012-02-14 WO PCT/EP2012/052513 patent/WO2012110512A1/de active Application Filing
- 2012-02-14 EP EP12705106.8A patent/EP2675817B8/de active Active
- 2012-02-14 US US13/985,755 patent/US20130328234A1/en not_active Abandoned
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US20060254461A1 (en) * | 2005-05-11 | 2006-11-16 | Agency For Science, Technology, And Research | Method and solution for forming anatase titanium dioxide, and titanium dioxide particles, colloidal dispersion and film |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JPWO2019138989A1 (ja) * | 2018-01-12 | 2020-12-24 | 日本化学工業株式会社 | チタンキレート化合物の製造方法 |
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WO2012110512A1 (de) | 2012-08-23 |
EP2675817B8 (de) | 2015-11-25 |
EP2675817B1 (de) | 2015-09-16 |
DE102011011544A1 (de) | 2012-08-23 |
EP2675817A1 (de) | 2013-12-25 |
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